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    • 专利摘要:
    The invention describes a new type of nickel complex and its method of preparation. The invention also relates to the use of said complex in an olefin transformation process.
    公开号:FR3020286A1
    申请号:FR1453817
    申请日:2014-04-28
    公开日:2015-10-30
    发明作者:Pierre Boulens；Pierre-Alain Breuil；Joost Reek；Helene Olivier-Bourbigou
    申请人:IFP Energies Nouvelles IFPEN；Universiteit Van Amsterdam ；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a new family of nickel-based complexes, and their method of preparation. The invention also relates to the use of said complexes as catalysts for reactions of chemical transformations.
    [0002] PRIOR ART: It is known to prepare transition metal-based complexes for their application in various fields of chemistry, particularly in the field of catalytic transformations such as hydroformylation, hydrogenation, cross-coupling, oligomerization. Olefins ...
    [0003] The preparation of such complexes requires the choice of metal and suitable ligands. Among these ligands, bidentate ligands are an important class of ligands used in the preparation of transition metal catalysts for various types of catalytic chemical transformations.
    [0004] EP 2 220 099 B1 discloses a coordination complex system comprising multidentate ligands having the formula: Ri-SO2-NH-P (XR2) 2; or R1-SO2-N = PH (XR2) 2, or R1-SO (OH) = NP (XR2) 2, wherein X is independently 0, S, NH, or a bond; wherein R1 and R2 are independently selected from a substituted or unsubstituted alkyl group and an aryl group, wherein at least one equivalent of ligand is complexed to one equivalent of a metal selected from rhodium, iridium, platinum, palladium and lanthanides. EP 2 220 099 B1 indicates that the coordination complex system can be used as a catalyst for hydroformylation, hydrogenation, hydrogenation, polymerization, isomerization, etc. The Applicant in his research has point a new family of nickel-based complexes and their method of preparation. It has been surprisingly found that such complexes exhibit interesting catalytic properties. In particular, these catalysts exhibit good activity in the oligomerization of olefins, more specifically in the dimerization of ethylene to butene-1. These complexes also have good selectivity in the dimerization of ethylene to butene-1. An object of the invention is to provide a new family of nickel-based complexes. Another object of the invention is to propose a new catalytic system comprising said complexes for chemical transformation reactions, in particular for the oligomerization of olefins. Detailed description of the invention Nickel complexes The complex according to the invention is a nickel-based complex corresponding to the formula (I) ## STR1 ## Wherein the P, N, S, O atoms constitute a ligand moiety; A and A ', which are the same or different, are independently O, S, NR3, or a single bond between the atom; of phosphorus and a carbon atom, - the R3 group is either a hydrogen atom or a cyclic or non-substituted or unsubstituted or cyclic alkyl group and optionally containing heteroelements, or an aromatic group, substituted or unsubstituted and containing or not hetero elements, the groups R 1, represented on the formula by R 1a and R 1b, with R 1 and R 1b being identical or different from each other, bound or non-linked to one another, are chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted, and whether or not containing heteroelements, aromatic groups, substituted or unsubstituted and whether or not containing heteroelements, the R2 group is chosen from cyclic or non-substituted or unsubstituted or cyclic alkyl groups and optionally containing heteroelements, substituted or unsubstituted aromatic groups and optionally containing identical heteroelements, L1 and L2, or different, represent a base of Lewis, - Xi is a carbon atom bonded to or part of at least one cyclic or non-cyclic alkyl group, unsaturated or unsaturated, substituted or unsubstituted and optionally containing heteroelements, a substituted aromatic group or no and containing or not containing hetero elements, - L1, L2 and X1 are such that the degree of oxidation of nickel is respected, and O represents the delocalization of the negative charge on the ligand fragment consisting of the P, N atoms, For the purposes of the present invention, the term "alkyl" denotes a linear or branched hydrocarbon-based chain containing from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms. Preferred alkyl groups are preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl. These alkyl groups may be substituted with heteroelements or groups containing heteroelements such as a halide, an alkoxy. By an "alkoxy" substituent is meant an alkyl-O- group in which the term alkyl has the meaning given above. Preferred examples of alkoxy substituents are methoxy or ethoxy. By "cyclic alkyl" is meant a monocyclic hydrocarbon group having a carbon number greater than 3, preferably between 4 and 24, more preferably between 6 and 12, preferably a cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl group. or polycyclic (bi- or tricyclic) having a carbon number greater than 3, preferably between 4 and 18, such as for example the adamantyl or norbornyl groups.
    [0005] By "linear unsaturated alkyl" or "cyclic unsaturated alkyl" is meant a linear or cyclic alkyl having at least one unsaturation, the term alkyl and cyclic alkyl having the meaning given above. By "aromatic" is meant an aromatic mono- or polycyclic group, preferably mono- or bicyclic, having a number of carbon atoms between 5 and 20. When the group is polycyclic, that is to say that it comprises more than one ring nucleus, the ring nuclei can advantageously be condensed two by two or attached two by two by links a. The aromatic group according to the invention may contain a heteroelement such as nitrogen, oxygen or sulfur.
    [0006] The term ligand according to the present invention is used interchangeably to mean one or more of the limiting forms of the ligand corresponding to formula la), 1 b) and / or 1c): ## STR1 ## In which - A and A ', which may be identical or different, are independently O, S, NR 3, or a single bond between phosphorus atom and a carbon atom, the group R3 is either a hydrogen atom or a cyclic or non-cyclic alkyl group, substituted or unsubstituted and optionally containing or not containing heteroelements, or an aromatic group, substituted or not and containing or not heteroelements, - the groups R1, represented on the formula by Ria and R1b, with Ria and Rlb being identical or different from each other, linked or not with each other, are chosen of the cyclic or non-cyclic alkyl groups, substituted or unsubstituted and containing or not containing heteroelements, the aromatic groups Whether substituted or unsubstituted and containing heteroelements or not, the group R2 is chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, substituted or unsubstituted aromatic groups and optionally containing heteroelements. The two groups R1 (Ria and Rb) may be identical or different from each other. These two groups Ria and Rb can also be linked together. In such a case, the two groups R 1 may correspond to groups such as bis-phenyl or bis-naphthyl. The ligands according to the invention may be prepared by a condensation reaction of a sulfonamide, for example para-n-butylphenylsulfonamide and a phosphine halide, such as Ph2PCI, in the presence of a Briinsted base. such as triethylamine for example, in a solvent. In solution, these ligands can (co) exist in the three forms la), 1b) or 1c) described above. L1 and L2, which are identical or different, whether linked together or not, represent a Lewis base. For the purposes of the present invention, the term "Lewis base" means any chemical entity of which one constituent has a doublet or more of free or non-binding electrons. The Lewis bases according to the invention correspond in particular to any ligand comprising an oxygen, nitrogen or phosphorus atom having a doublet of free or non-binding electrons, or a double bond 7 capable of forming with nickel. n2 type coordination.
    [0007] The L 2 group of the complex of formula (I) according to the invention may represent a phosphine of type P (Al R, ia) (A, 1R) (ic1 / 4'1R, 1c) or a phosphinamine of type (RAi) (R, ibA, i) p_NH (R, 2) or (Rp1 / 41) (RA, i) p -NH_s (O) 2 (-2,), in which: - Al, A'l and A " 1, which are identical or different from one another, are independently O, S, NR 3, or a single bond between the phosphorus atom and a carbon atom; the R 3 group is either a hydrogen atom, a cyclic alkyl group or no, substituted or unsubstituted and optionally containing heteroelements, or an aromatic group, substituted or unsubstituted and containing heteroelements or not, - the groups R'1 is Fila, R'lb and Filc being identical or different from each other, bound or between each other, are chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, aromatic groups, substituted or unsubstituted and optionally containing heteroelements, - the R'2 group. t selected from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, substituted or unsubstituted aromatic groups and optionally containing heteroelements. When the group X 1 is a carbon atom bonded to or part of at least one linear or cyclic unsaturated alkyl group, X 1 and L 1 are advantageously linked so as to form an allyl fragment of a linear or cyclic alkyl allowing a binding of type 7 nickel-allyl. According to the invention, the groups R 'is Ria and R113, identical or different, linked or not to each other, and the R'1 groups Fila, R'lb and Filc, identical or different, linked or not to each other, are independently chosen from alkyl groups comprising 1 to 15 carbon atoms, the aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not. Preferably, the groups R1, Ria and R113 being identical or different, bonded or not to each other, and the R'1 groups, ie Fila, R'lb and Filc being identical or different, linked or not to each other, are independently selected from among methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl, adamantyl, substituted or unsubstituted, containing or not containing heteroelements; the phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl and 2-isopropoxyphenyl groups, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or unsubstituted, containing heteroelements or not. In the case where the groups R 1 is Ria and Rib identical or different are bonded together, these groups may correspond to groups such as bis-phenyl, bis-naphthyl. In the case where the R'l groups, which are identical or different, are linked together, these groups may correspond to groups such as bis-phenyl or bis-naphthyl.
    [0008] According to the invention, the groups R2 and the groups R'2, which are identical or different, are independently chosen from alkyl groups comprising 1 to 15 carbon atoms, the aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
    [0009] Preferably, the groups R 2 and the groups R '2, which are identical or different, are independently chosen from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl and pentyl groups. substituted or unsubstituted cyclohexyl, adamantyl, containing heteroelements or not; phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditertbutyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-bis (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or no, containing heteroelements or not.
    [0010] Preferably, the group R 3 is either a hydrogen atom or an alkyl group. The complex according to the invention may be prepared by contacting at least one ligand comprising the ligand fragment consisting of the P, N, S and O atoms corresponding to formula (1a), (1b) or ( 1c) as defined according to the invention, with at least one oxidation state nickel precursor (0), a precursor of the Xl group, a precursor of the group Let optionally a precursor of the Lewis base group L2. The presence of the Lewis base group L 2 is, for example, optional when a second equivalent of the ligand is used. In this case, the ligand according to the invention plays the role of a Lewis base. Advantageously, the precursors of the groups X1 and L1 can come from the nickel precursor (0). This is the case, for example, when the precursors of the groups X 1 and L 1 form between them a linear or cyclic unsaturated alkyl. Preferably, said linear or cyclic unsaturated alkyl is a diene. The complex according to the invention may be prepared by contacting at least one ligand comprising the ligand fragment consisting of the P, N, S and O atoms corresponding to formula (1a), (1b) or ( 1c) as defined according to the invention, with at least one oxidation state nickel precursor (+ II), in the presence of a precursor of the group X1, a precursor of the group L1, a reducing agent and optionally a precursor of the Lewis L2 base group. The presence of the Lewis base group L 2 is, for example, optional when a second equivalent of the ligand is used. In this case, the ligand according to the invention plays the role of a Lewis base. In the case where a nickel precursor of oxidation state (+ II) is used in the presence of a reducing agent, any agent leading to the reduction of nickel known to those skilled in the art can be used. The reducing agent may be selected from NaBH4, LiAIH4, AlEt3, Na, K, KC8 and dihydrogen.
    [0011] The preparation temperature of the complex according to the invention may vary between -80 ° C. and 130 ° C. The preparation of the complex according to the invention can be carried out in the presence or absence of solvent. Preferably, the preparation is carried out in the presence of a solvent. The preparation solvent may be chosen from organic solvents and in particular from ethers, alcohols, chlorinated solvents and saturated, unsaturated, aromatic or non-aromatic hydrocarbons, cyclic or otherwise. Preferably, the solvent is chosen from hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, the monoolefins or diolefins preferably containing 4 to 20 carbon atoms, cycloocta-1,5- diene, benzene, toluene, ortho-xylene, mesitylene, ethylbenzene, dichloromethane, chlorobenzene, methanol, ethanol, pure or in admixture, and ionic liquids. In the case where the solvent is an ionic liquid, it is advantageously chosen from among the ionic liquids described in US Pat. Nos. 6,951,831 B2 and FR 2,895,406 B1. The complex according to the invention comprises a nickel of degree of oxidation (+ I) or (+11), preferably a nickel of degree of oxidation (+11). The complexes according to the invention can also form multi-nuclear aggregates.
    [0012] When the nickel precursor has a degree of oxidation (0), the latter may be chosen from nickel (0) bis (cycloocta-1,5-diene), nickel (0) bis (cycloocta-1,3- diene), nickel (0) bis (cyclooctatetraene), nickel (0) bis (cycloocta-1,3,7-triene), bis (otolylphosphito) nickel (0) (ethylene), nickel (0) tetrakis (triphenylphosphite), nickel (0) tetrakis (triphenylphosphine), and nickel (0) bis (ethylene), alone or in admixture. Said nickel precursors may optionally be complexed with Lewis bases. When the nickel precursor is of oxidation state (+11), the latter can be chosen from nickel chloride (11), nickel (II) chloride (dimethoxyethane), nickel bromide (11), nickel (II) bromide (dimethoxyethane), nickel fluoride (11), nickel iodide (11), nickel sulphate (11), nickel carbonate (11), nickel dimethylglyoxime (11) , nickel hydroxide (11), nickel hydroxyacetate (11), nickel oxalate (11), nickel carboxylates (11) such as, for example, 2-ethylhexanoate, nickel phenates (11), ), nickel acetate (11), nickel trifluoroacetate (11), nickel triflate (11), nickel acetylacetonate (11), nickel hexafluoroacetylacetonate (11), allyl nickel chloride (11), 11), allyl nickel bromide (11), methallylnickel chloride dimer (11), allyl nickel hexafluorophosphate (11), methallyl nickel hexafluorophosphate (11), nickel biscyclopentadienyl (11), bisallyl nickel (11) and bismethallyl nickel (11); in their hydrated form or not, taken alone or in mixture. Said nickel precursors may optionally be complexed with Lewis bases. We present below some examples of complexes of formula (I) according to the invention as well as the operating conditions by means of which they were obtained. These examples are for illustrative purposes and are in no way limiting the scope of the invention. In the example of Scheme 1, the addition of 2 equivalents of ligand Li, to one equivalent of nickel (0) bis (cycloocta-1,5-diene) (Ni (COD) 2) in 1,5-cyclooctadiene The complex is prepared at a temperature of between -40 ° C. and room temperature (RT) for 16 hours. The Cl complex is characterized by 3 'P NMR by a large singlet at 54 ppm. 1 HN-PPh 2 2 nBu Ni (Cod) 2 to 1.5-COD, -40 ° C to RT, 16h nBu nBu o ii, S '- Ph N = P C H Ni, O / 0 Another type of complex of formula (I) according to the invention is prepared by adding an equivalent of L2 or L3 ligand and an equivalent of N (diphenylphosphino). isopropylamine ((iPr) NHPPh2) or N- (diphenylphosphino) -propylamine ((nPr) NHPPh2) to one equivalent of nickel (0) bis (cycloocta-1,5-diene) in toluene or chlorobenzene. , C3, C4 and C5 are obtained at a temperature between 0 ° C and 50 ° C after a period of 1 to 16 hours (Diagram 2) The complexes are characterized in 3'M NMR by two doublets with a coupling constant of the order of 30 Hz.
    [0013] Scheme 2 00 + iPr-NH-PPh 2 Ni (cod) 2 ao 0 V / HS F3C-S '8-Pr F3C I-e ----) NP eH Ni, NP KPh Phiiz, h Toluene, TA at 50 ° C, 1 hr. C220 v / H p F3C N Chlorobenzene, TA, 6h + nPr-NH-PPh2 Ni (cod) 2 Io F3C -S%. ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR1 ## ## STR2 ## ## STR2 ## tolyl L3 O00 / O-T0IYI p F3C N + -H2-o-tolyl L3 nPr-NH-PPh2 Ir Chlorobenzene, 0 ° C to RT, 4h Ni (cod) 2 O n F3C o-tolyl ## STR1 ## Scheme 3 illustrates, by the bisnaphthol group, two complexes of formula ## STR2 ## wherein: ## STR2 ## (I) in which the Ria and Rib substituents are bonded together, A = O and in which the R2 group is a 4-n-butyl phenyl (C6) group or a -CF3 (C7) group. The C6 and C7 complexes are prepared by adding one equivalent of the ligand L4 or L5 (here represented with one equivalent of Et3N) respectively and one equivalent of trimethylphosphine to one equivalent of nickel (O) bis (1,5-cycloocta) -diene) in chlorobenzene. The complexes are obtained after 3 hours at room temperature (RT).
    [0014] Scheme 3 nBu nBu "- Chlorobenzene TA, 3h Ni (cod) 2 + PMe3 L4 C6 + PMe3 Ni (cod) 2" - Chlorobenzene TA, 3h L5 C7 Similar complexes C8, C9 and C10, having a trimethylphosphine ligand, are obtained under the same conditions with the respective ligands Li, L2 and L3 (scheme 4). These complexes are characterized in 31P NMR by two doublets with a coupling constant of the order of 30 Hz. Scheme 40 ## EQU1 ## PMe3 L1 C8 00 + PMe3 0 0 v / H S'p F3Cv N --- Ni (C0C1) 2 F3C-S: / 5- Pr 11- , I Pr N = P,, 1, .. '^ Toluene , 0 ° C to RT, 16h Ni, -Ple s I L2 C9 Ni (c0d) 2 w Chlorobenzene TA, 15min 0 n Il - / 0-tOly1% / o-tolyl / F3C-S 'NP,,' Preferably, the complexes according to the invention have the following formulas: ## STR2 ## ## STR2 ## wherein R 1 is R 2 R 2 R 2 R 2 R 2 R 2 R 2 R 2 R 2 R 2 R 2 R 2 R 1 2 ARla AIRlb -P 0 H NP R'2 / A'1 RIIb 0 II ARla 15- I Wing N. N = P Ki Rob II R'ic in which the nickel is of oxidation degree (+ II ), Δ represents the delocalization of the negative charge on the ligand fragment consisting of the atoms P, N, S and O and A, A ', A1, I1 / 4.1, A "1, Ria, Rib, R a, R, R, ib, R2 and meet the specifications of the invention.
    [0015] A non-exhaustive list of ligands that may be suitable for the preparation of the complexes according to the invention is shown below. The ligands are here represented in their limiting forms la) and 1b). ## EQU1 ## = PHPr2 ----, .. o 0 O 2; ^, S F3C " N = PHPh2 H N 0 S /% 0% S 0 0 N = - PHPh2, -0 Bu 0% 0 S N = PHPr2 0% 0 S N = PHEt2 0% 0 e HN-PEt2 0% 20 S HN-PPh2 0 0% 0% 0-SS HN-PPh2 NN = PHPh2 us /% 00 0% 2) S N, --- PHPh2 0% 20, S F3C " HN-PPr2 0% 2) S HN-PPr2 0 O 20, S F3C" N = PHPr2 0%; ^% 0 ## STR2 ## 0% (:: ^ S HN-PCY2 0% 0 S N = PHCy2 0% 2; ^ S HN-PBu2 0% (:: ^ S N = PHBu2 0% 0 S N = - PHBu2 0 0 0 0% 0% 0% 0% 0, S, S F30 S, S F30 F30 N = - PHCy2 F30, N = PHBu2 HN-PCY2 HN-PBu2 0% 0 e, Ph HN -P Bu 0% 0 S, Ph HN-F ' Bu 0% 2) S ph F3C NP H / Bu 0% 2) S hp /. .. N = PH Bu 0% 20 S / Ph N = PH Bu 0% 2) S ph N = PH Bu 0% 2; ^ S ph / 1 11 N = -PH Bu, Ph HN-P Bu Using the complexes of formula (I) in a reaction of transfor The nickel-based complexes of formula (1) according to the invention can be used as a catalyst in a chemical transformation reaction, such as the reaction of hydrogenation, hydroformylation, cross-coupling or oligomerization of olefins. . In particular, these complexes are used in a process for oligomerizing an olefin feed advantageously having 2 to 10 carbon atoms.
    [0016] Preferably, the oligomerization process is a process for dimerizing ethylene to butene-1. The nickel complex of formula (1) according to the invention may be used in the form of a catalytic composition, mixed with a compound known as an activating agent. Said activating agent is advantageously chosen from the group formed by tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbylaluminium compounds, aluminum halides, aluminoxanes, organoboron compounds, organic compounds capable of giving or to capture a proton, taken alone or mixed.
    [0017] Tris (hydrocarbyl) aluminum, chlorinated or brominated hydrocarbylaluminum compounds and aluminum halides preferably correspond to the general formula AlxRyW, in which R represents a monovalent hydrocarbon radical containing, for example, up to 12 carbon atoms, such as alkyl, aryl, aralkyl, alkaryl or cycloalkyl, W represents a halogen atom chosen for example from chlorine and bromine, W being preferably a chlorine atom, x is 1 to 2, y and z are value of 0 to 3. Examples of such compounds include ethyl aluminum sesquichloride (Et3Al2C13), methylaluminum dichloride (MeAIC12), ethylaluminum dichloride (EtAIC12), isobutylaluminum dichloride (iBuAlC12), diethylaluminum chloride (Et2AlCl), trimethylaluminum, tributylaluminum, tri-n-octylaluminum and triethylaluminum (Al Et3).
    [0018] In the case where said activating agent is chosen from aluminoxanes, said activating agent is advantageously chosen from methylaluminoxane (MAO), ethylaluminoxane and modified methylaluminoxanes (MMAO). These activating agents can be used alone or as a mixture.
    [0019] Preferably, said activating agent C is chosen from dichloroethylaluminum (EtAIC12) and methylaluminoxane (MAO). In the case where said activating agent is chosen from organoboron compounds, said activating agent is preferably chosen from Lewis acids of tris (aryl) borane type such as tris (perfluorophenyl) borane, tris (3,5-bis (trifluoromethyl) phenyl) borane, tris (2,3,4,6-tetrafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluobiphenyl) borane and their derivatives and (aryl) borates associated with a triphenylcarbenium cation or a trisubstituted ammonium cation such as triphenylcarbenium tetrakis (perfluorophenyl) borate, N, N-dimethylanilinium tetrakis (perfluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate.
    [0020] In the case where said activating agent is chosen from organic compounds capable of giving a proton, said activating agent is preferably chosen from the acids of formula HY in which Y represents an anion. In the case where said activating agent is chosen from organic compounds capable of capturing a proton, said activating agent is preferably chosen from Bronsted bases. The solvent of the oligomerization process may be chosen from organic solvents and preferably from ethers, alcohols, chlorinated solvents and saturated or unsaturated hydrocarbons, aromatic or otherwise, cyclic or otherwise. In particular, said solvent is chosen from hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, the monoolefins or diolefins preferably comprising 4 to 20 carbon atoms, cycloocta-1,5- diene, benzene, toluene, ortho-xylene, mesitylene, ethylbenzene, dichloromethane, chlorobenzene, methanol, ethanol, pure or in admixture, and ionic liquids. In the case where said reaction solvent is an ionic liquid, it is advantageously chosen from the ionic liquids described in US Pat. No. 6,951,831 B2 and FR 2,895,406 B1. Oligomerization is defined as the conversion of a monomer unit into a compound or mixture of compounds of the general formula CpH2p with 4 p 80, preferably with 4 p 50, more preferably with 4 p 26 and more preferably with The olefins used in the oligomerization process are olefins having from 2 to 10 carbon atoms. Preferably, said olefins are chosen from ethylene, propylene, n-butenes and n-pentenes, alone or as a mixture, pure or diluted. In the case where said olefins are diluted, said olefins are diluted with one or more alkanes, as found in "slices" from petroleum refining processes, such as catalytic cracking or cracking. steam. Preferably, the olefin used in the oligomerization process is ethylene. Said olefins can come from non-fossil resources such as biomass. For example, the olefins used in the oligomerization or dimerization process according to the invention may be produced from alcohols, and in particular by dehydration of the alcohols. The concentration of nickel in the catalyst solution is advantageously between 1 × 10-8 and 1 mol / L, and preferably between 1 × 10 -6 and 1 × 10 -2 mol / L.
    [0021] The oligomerization process advantageously operates at a total pressure of between atmospheric pressure and 20 MPa, preferably between 0.1 and 8 MPa, and at a temperature between -40 and + 250 ° C., preferably between -20 ° C. C and 150 ° C.
    [0022] The heat generated by the reaction can be removed by any means known to those skilled in the art. The oligomerization process can be carried out in a closed system, in a semi-open system or continuously, with one or more reaction stages. Sturdy stirring is advantageously carried out to ensure good contact between the reagent (s) and the catalyst system. The oligomerization process may be carried out batchwise. In this case, a selected volume of the solution comprising the complex according to the invention is introduced into a reactor provided with the usual stirring, heating and cooling devices. The oligomerization process can also be carried out continuously. In this case, the solution comprising the complex according to the invention is injected at the same time as the olefin in a reactor stirred by conventional mechanical means or by an external recirculation, and maintained at the desired temperature. The catalyst composition is destroyed by any usual means known to those skilled in the art, then the reaction products and the solvent are separated, for example by distillation. The olefin that has not been transformed can be recycled to the reactor. The process according to the invention can be carried out in a reactor with one or more reaction stages in series, the olefinic feedstock and / or the pre-conditioned catalytic composition being introduced continuously, or in the first stage, either in the first and any other floor. At the outlet of the reactor, the catalytic composition can be deactivated, for example by injection of ammonia and / or an aqueous solution of sodium hydroxide and / or an aqueous solution of sulfuric acid. Unconverted olefins and alkanes optionally present in the feed are then separated from the oligomers by distillation.
    [0023] The products of the present process can find application as, for example, automotive fuel components, fillers in a hydroformylation process for the synthesis of aldehydes and alcohols, as components for the chemical, pharmaceutical or perfume industry and or as fillers in a metathesis process for the synthesis of propylene for example.
    [0024] The following examples illustrate the invention without limiting its scope. The notation Cy represents the cyclohexyl group.
    [0025] Example 1 Synthesis of N- (diphenylphosphino) isopropylamine ((iPr) NHPPh2) according to the method described in WO2008 / 077908.
    [0026] N-H 2 1 H Isopropylamine (1.8 mL, 22.3 mmol, 2 eq (equivalents) and triethylamine (4.66 mL, 33.4 mmol, 3 eq.) Are placed in a Schlenk with 10 mL of tetrahydrofuran ( THF) To this mixture is added dropwise chlorodiphenylphosphine (2 mL, 11.14 mmol, 1 eq.) The mixture is stirred for 10 minutes (min) at room temperature and the precipitate formed is filtered. is dried under vacuum to give a colorless oil Trituration of the oil in pentane produces a white powder This powder is rinsed with 2 × 10 ml of pentane 2.1 g of white powder is isolated, a yield of 75%. The pure product is obtained by distillation of the solid at low pressure The product is characterized by 31P NMR spectroscopy (C6D6), 1H NMR (C6D6) and 13C NNAR (C6D6) 31P NMR (C6D6): 34.94.
    [0027] Synthesis of N- (diphenylphosphino) -n-propylamine ((nPr) NHPPh) according to the method described in WO2008 / 077908. H 1 N PPh 2 N-propylamine (3 mL, 2.17 g, 36.7 mmol, 3 eq) is mixed with THF (10 mL). To this mixture is added dropwise chlorodiphenylphosphine (2 mL, 2.46 g, 11.1 mmol, 1 eq.). After stirring for 10 minutes at room temperature, the mixture is filtered and the liquid phase collected. The liquid phase is evaporated under reduced pressure to give a light yellow oil (isolated: 2.3 g, 85%). Synthesis of ligands L1, L2, L4, L5.
    [0028] The synthesis of ligands L1, L2, L4 and L5 was carried out according to the method described in the literature: F. G. Terrade, Eur. J. Inorg. Chem. 2014, 1826-1835 Synthesis of Ligand L3 metamorphos (o-toly1) 0 M / F3C-SN M L3.Et3N Trifluoromethanesulfonamide (2.4 g, 16 mmol, 1 eq.) And triethylamine (4.2 g, 40 mmol, 2.6 eq., 6 mL) are solubilized in 30 mL of THF. In a second Schlenk, di (o-tolyl) chlorophosphine is solubilized with 10 mL of THF. The chlorophosphine solution (4 g, 16 mmol, 1 eq) in 10 mL of THF is added dropwise to the sulfonamide solution to produce a white precipitate. After 20 min, the mixture is filtered and the solid is rinsed twice with 10 mL of THF. The liquid phase is evaporated under vacuum to obtain a colorless oil. 20 ml of diethyl ether are added to said oil to precipitate a white powder. The powder is rinsed three times with 5 mL of diethyl ether. After drying under vacuum, 2.52 g of powder is obtained, ie a yield of 68%. The product is characterized by 3113i spectroscopy, 1. 1H NMR (C6D6), 31P NMR (C6D6), 1H NMR (C6D6) and 13C NMR (C6D6). 31P NMR (C6D6): 15.77 (s, PH 12% form); 22.62 (broad ss, NH-NEt3 form, 88%) Synthesis of the complex Cl nBu 0 0 Ph N = P e H Ni , '-' 0 NP S% millet Ph 0 nBu Cl Li ligand 4-nBu-Bz-SO2-NH-PPh2, 397 mg, 1 mmol, 2 eq.) And Ni (COD) 2 are solubilized in dry 1,5-cyclooctadiene (10 mL) and the mixture is stirred for 16 hours. hours (h) until the ligand signal disappears by phosphorus NMR. The solvent is evaporated to give a dark green oil. This oil is triturated with pentane several times to remove traces of cyclooctadiene. The oil is then extracted with a mixture of heptane / toluene (4: 1) and the solvent fractions are collected and evaporated to give an orange solid in powder form. The powder is washed twice with 10 ml of pentane to obtain an orange powder (131 mg, isolated yield: 27%). 31p NMR (C6D6): 54.06 Elemental Analysis Found (theoretical): C: 64.17 (64.94); H: 6.64 (6.29); N: 3.15 (2.91). Synthesis of the complex C2 0 n Pr F3C-S, '' / s /, Pr N_P P c) H Ni, IN-r Ph / Ph C2 The ligand L2 (F3C-SO2-N = P (iPr) 2H, 395 mg, 1.5 mmol, 1 eq.), N (diphenylphosphino) isopropylamine (365 mg, 1.5 mmol, 1 eq.) And Ni (COD) 2 ( 413 mg, 1.5 mmol, 1 eq.) Are placed in a Schlenk and solubilized in 30 ml of toluene to which 4 drops of 1,5-cyclooctadiene are added, the solution is then heated at 50 ° C. for 20 minutes. This solid is triturated in pentane (10 mL) and then the pentane is removed by syringe The operation is repeated once to give a solid and then washed with 3 × 10 mL of pentane. dissolved in toluene and filtered on a syringe disk to remove the solid residues and the filtrate thus obtained is evaporated off The powder obtained is triturated in pentane and then washed with 2 x 10 ml of pentane and finally dried under vacuum. is obt inactive (isolated yield: 574 mg, 57%). 31p NMR (C6D6): 85.76 (d, J = 30.9 Hz); 60.22 (d, J = 31.3 Hz) Elemental analysis found (theoretical): C 42.39 (42.54); H: 7.26 (7.14); N: 2.68 (2.76).
    [0029] Synthesis of the complex C3 0 r, F3C-S, "3- Pr, I Pr N = P" H Ni, NP / / Ph / Ph - C3 The ligand L2 (F3C-SO2-N = P) iPr) 2H, 265 mg, 1 mmol, 1 eq.), N- (diphenylphosphino) -n-propylamine (243 mg, 1 mmol, 1 eq.) and Ni (COD) 2 (275 mg, 1 mmol). , 1 eq.) Are placed in a Schlenk and solubilized in 20 ml of chlorobenzene to which 0.5 ml of 1,5-cyclooctadiene are added The solution is left to stir for 6h at room temperature and the solvent is then evaporated under reduced pressure to give a This solid is triturated and then washed with 2 × 10 ml of pentane, the powder is then dried under vacuum and then suspended in 5 ml of toluene.The solvent is evaporated and the operation is repeated once giving a very little powder. Soluble in toluene The powder is then dissolved in 5 mL of dichloromethane and the solution is filtered through a 0.2 micron syringe disc to remove the insolubles.The dichloromethane is evaporated and then 5 mL of toluene. e are added which are in turn evaporated under vacuum. Canary yellow powder is obtained (isolated: 325 mg, 47%). 31p NMR (CD2Cl2): 64.54 (d, 2 Jpp = 31 Hz); 92.16 (d, 2 Pd = 31 Hz). Synthesis of the complex C 4 O 11 / m-tolyl F 3 C -S 3 -H 2 O-tolyl N = P 9 H Ni, NF KPh / Ph C4 L3 ligand (463 mg, 1 mmol, 1 eq.), N- (diphenylphosphino) isopropylamine (244 mg, 1 mmol, 1 eq.) And Ni (COD) 2 (275 mg, 1 mmol, 1 g) eq.) are solubilized in 20 mL of chlorobenzene at 0 ° C. The mixture is stirred at room temperature for 16 hours to give a dark solution.The solvent is evaporated under reduced pressure to give a dark oil.The oil is triturated in diethyl ether (10 mL) and the solvent is removed using a syringe.The operation is repeated twice which provides a yellow powder which is washed with 0 ° ether Until the ether phase is no longer dark The solid is then dried under vacuum to give the product (190 mg isolated: 25% yield) 31p NMR (C6D6): 52.13 (d, 2 Jpp = 23.1) Hz) 62.82 (d, 2 Jpp = 23.3 Hz) Elemental analysis found (theoretical): C: 51.62 (59) 5.25 (5.88); 3.22 (3.63). Synthesis of the complex C 5 O 11 / -J o-tolyl F 3 C -S: n -O-toly-8-N = P, H-NP Ph Ph C5 L3 ligand (463 mg, 1 mmol, 1 eq.) Of N- (diphenylphosphino) -n-propylamine (243 mg, 1 mmol, 1 eq.) And Ni (COD) 2 (275 mg. 1 mmol, 1 eq.) Are solubilized in 15 mL of chlorobenzene at 0 ° C. The mixture is stirred at ambient temperature for 4 hours to give a dark brown solution. The solvent is evaporated under reduced pressure to give a dark oil. The oil is triturated and washed with pentane (7 x 5 mL) resulting in the formation of a dark yellow solid which is dried under vacuum. This solid is then washed with diethyl ether at 0 ° C (3 x 10 mL). The ether is evaporated under reduced pressure and the powder is then suspended in 5 ml of toluene which is evaporated under reduced pressure. The operation is repeated once and leads to a light yellow powder (isolated 280 mg, 36%). 31 NMR (CD2Cl2): 52.33 (d, 2 Jpp = 24.7 Hz); 65.09 (d, 2 Jpp = 24.5 Hz). Synthesis of the C6 nBu Complex The L4 ligand (4-nBu-C6H4-802-NH-P ((R) -Binol) isolated with one equivalent of triethylamine, 53 mg, 0.1 mmol, 1 eq.) And Ni (COD 2 (28 mg, 0.1 mmol, 1 eq.) Are solubilized in chlorobenzene (3 mL). To this solution is added a solution of trimethylphosphine (10% in toluene, 1011L, 0.1 mmol, 1 eq.). The solution quickly turns brown and is stirred for 3 h at room temperature. The solvent is evaporated to give a brown solid which is triturated and washed with 3 x 5 mL of pentane.
    [0030] The solid is dried giving a yellow powder: isolated yield 35%. Two diastereoisomers (a) and (b) are formed in a 1: 1 ratio. 31p NMR (C6D6): (a) -13.4 (d, 2Jpp = 36Hz) and 155.3 (d, 2Jpp = 36Hz) (b) -12.7 (d, 2Jpp-cis = 39Hz) and 156.2 (d, 2Jpp) = 39 Hz). Synthesis of the complex C7 F3C00, S13-N-C7 The L5 ligand (F3C-NH-P ((R) -Binol, isolated with a triethylamine equivalent, 46 mg, 0.1 mmol, 1 eq.) And Ni (COD) 2 (28 mg, 0.1 mmol, 1 eq.) Are solubilized in chlorobenzene (3 mL) To this solution is added a solution of trimethylphosphine (10% in toluene, 1011L, 0.1 mmol, 1 eq. The solution quickly turns brown and is stirred for 3h at room temperature The solvent is evaporated to give a brown solid which is triturated and washed with 3 x 5 mL of pentane The solid is dried giving a yellow powder: isolated yield 35% Two diastereoisomers (a) and (b) are formed in a 1: 1 ratio 31 NMR (C6D6): (a) -14.2 (d, 2Jpp = 33 Hz) and 157.6 (d, 2Jpp = 33 Hz) (b) 13.6 (d, 2 Jpp-cis = 36 Hz) and 158.0 (d, 2 Jpp = 36 Hz) Synthesis of the C8 nBu C8 complex The Li ligand (4-nBu-C6H4-SO2-NH-PPh2, 390 mg, 1 mmol, 1 eq) and trimethylphosphine (1M solution in toluene, 1 mL, 1 mmol, 1 eq. in a Schlenk and solubilized in 30 mL of toluene. In another Schlenk of Ni (COD) 2 (270 mg, 1 mmol, 1 eq) is solubilized in 20 mL of toluene. Both solutions are cooled in a water / ice bath and the solution containing the phosphines is added by cannula to the nickel solution. After addition, the mixture is allowed to rise to room temperature and stirred for 20 minutes. It is finally heated at 60 ° C for 1 hour to give a dark brown liquid. The solvent is then evaporated to give an orange powder. The solid is washed with pentane to give an orange powder: isolated yield 36%. 31p NMR (C6D6): 60.25 (d, 2 Jpp = 26.7 Hz); -0.11 (d, 2Jpp = 26.7 Hz) Elemental analysis found (theoretical): C 61.67 (61.69); H: 6.87 (7.08); N: 2.27 (2.19). Synthesis of the complex C9 0 0 -F3C-11 / S: Pr1 Pr N = P1 () Ni, L2 L2 (F3C-SO2) N = P (iPr) 2H, 106 mg, 0.4 mmol, 1 eq) and trimethylphosphine (1M solution in toluene, 0.5 mL, 0.5 mmol, 1.25 eq.) Are placed in a Schlenk with 30 mL of toluene. another Ni (COD) 2 Schlenk is solubilized in 20 ml of toluene, the two solutions are cooled in a water / ice bath and the solution containing the phosphines is added to the nickel solution. then the solvent is evaporated to give a yellow powder which is triturated and then washed with 3 x 10 mL of pentane and dried under vacuum 31P NMR (C6D6): 86.8 ppm (d, P (iPr) 2 2 Pd = 31.05 Hz); -11.4 ppm (d, P (Me) 32 Jpp = 31.45 Hz). Synthesis of the complex C10 Ph 0 v ', n 0 -toly1 F3C-S1 :: 3 / o-toly1 N = P The L3 ligand (463 mg, 1 mmol, 1 eq.) And Ni (COD) 2 (275 mg, 1 mmol, 1 eq.) Are solubilized in s 20 mL of chlorobenzene. To this solution is added trimethylphosphine (1M in toluene, 1 mL, 1 mmol, 1 eq.). The mixture is left stirring for 15 minutes leading to a dark solution. The solvent is then removed under reduced pressure to give a dark solid. The solid is triturated with 20 ml of pentane to give a yellow powder and a colored solvent in violet. The solid is then rinsed with pentane until the purple color disappears. The solid is dried under vacuum to give a yellow powder: isolated yield 53%. 31p NMR (C6D6): -15.10 (d, 2 Jpp = 25.8 Hz); 54.75 (d, 2 Pd = 25.8 Hz). Elemental Analysis Found (Theoretical): C: 51.57 (51.68); H: 5.89 (6.00); N: 2.47 (2.33).
    [0031] Synthesis of the C11 PhI / (PNNiVPh IO / PPh3 C11 Complex The C11 reference complex is synthesized in accordance with the literature (Organometallics 1986, 5, 2356-2359) and the characterizations are in accordance with the expected product.
    [0032] Example 2: Oligomerization of ethylene The oligomerization reaction of ethylene was evaluated with the complexes Cl, C2, C4, C8 and C9 (10 moles) with the C11 complex as comparative example. The results obtained are reported in Table 1.
    [0033] The 250 ml reactor is dried under vacuum at 130 ° C. for 2 hours and then pressurized with 0.5 MPa of ethylene. The temperature is lowered to 20 ° C, then the ethylene overpressure is removed to reach 0.1 MPa. The solvent is added (45 mL of toluene), and the internal temperature set point is set (40 ° C or 80 ° C). Once the internal temperature is stabilized, the complex is introduced (10 μmol in 5 ml of toluene). Then the reactor is pressurized with ethylene at 3 MPa. Stirring (1000 rpm) is started (t = 0). After the defined reaction time, the mixture is cooled to 30 ° C with stirring, the reactor is depressurized and the liquid and gas phases are analyzed by gas chromatography (GC).
    [0034] The productivity (goligAgNi.h) is expressed as the mass of oligomers produced (in grams) per nickel mass used per hour.
    [0035] Table 1. Oligomerization of Ethylene with Various Complexes (30 bar ethylene) Com-Tempered Mass of Productivity Times Distribution of Products Butene-Hexeneplexe Rature oli gomers Reaction (poide 1 ["1 (g) ( min) C4 c, c, Cl 40 ° C 4.4 90 4956 92.7 6.6 0.7 99.7 95.5 Cl 80 ° C 5.8 90 6588 86.2 12.1 1.7 99.4 91.9 C2 40 ° C 10.2 90 11632 35.1 28.1 36.8 99.7 98.8 C4 40 ° C 23.9 90 Load 27187 86.3 11.9 1.8 98.0 81.7 C8 80 ° C 7.6 90 8601 86.4 12.1 1.5 98.3 90.5 C9 40 ° C 5.8 90 6638 37.4 28.8 33.8 99.7 99.0 C11 (50 mol) 40 ° C 32 130 5218 1.2 2.4 96.4 76.7 96.4 a Determined by GO percentage weight of cuts 04, 06 and C8 + with respect to all oligomers) Percentage weight of butene-1 in section 04. The above examples demonstrate that the complexes according to the invention have a good activity for the oligomerization of ethylene.
    权利要求:
    Claims (16)
    [0001]
    CLAIMS1 Nickel-based complex corresponding to the formula (I) ## STR5 ## wherein: P, N, S atoms, 0 constitute a ligand fragment, - A and A ', which are identical or different, are independently 0, S, NR3, or a single bond between the phosphorus atom and a carbon atom, - the R3 group is either an atom of hydrogen, whether or not a cyclic alkyl group, substituted or unsubstituted and optionally containing heteroelements, or an aromatic group, substituted or unsubstituted and optionally containing heteroelements, - the groups R 1, represented on the formula by Ria and R 1b , with Ria and Rb being identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-substituted or unsubstituted or substituted alkyl groups and optionally containing heteroelements, aromatic groups, substituted or unsubstituted and containing or not containing heteroelements, the group R2 is chosen from among the cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, or substituted or unsubstituted aromatic groups containing or not containing heteroelements, 20-L1 and L2, which may be identical or different, represent a Lewis base, - X1 is an atom of carbon bound to or belonging to at least one cyclic or non-cyclic alkyl group, unsaturated or unsaturated, substituted or unsubstituted and optionally containing heteroelements, substituted or unsubstituted aromatic group and optionally containing heteroelements, - L1, L2 and X1 are such that the degree of oxidation of nickel is respected, and O-represents the delocalization of the negative charge on the ligand fragment constituted by the P, N, S and O atoms.
    [0002]
    2. Complex according to claim 1, wherein L2 represents a phosphine of laxA, 1Rxic1 / 4'1R, i lap1 / 41) (R, A, i) p_b type P (Al R 'c) or a phosphinamine of type (R 'NH (R'2) or (Rp1 / 41) (R rt) A, i) p-NH_s (O) 2 (-, 2s, in which: - A1, A'1 and A "1, identical or different from each other, are independently O, S, NR 3, or a single bond between the phosphorus atom and a carbon atom, - the R 3 group is either a hydrogen atom, a cyclic alkyl group or not, substituted or not and containing or not containing heteroelements, or an aromatic group, substituted or not and containing or not heteroelements, - the groups R'1 is R'la, R'lb and Filc are identical or different from each other, linked or not between them, are chosen from cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, aromatic groups, substituted or unsubstituted and optionally containing heteroelements, - the group R'2 is selected if, among the cyclic or non-cyclic alkyl groups, substituted or unsubstituted and optionally containing heteroelements, substituted or unsubstituted aromatic groups and optionally containing heteroelements.
    [0003]
    A complex according to claim 1 or 2 wherein when X 1 is a carbon atom bonded to or part of at least one linear or cyclic unsaturated alkyl group, X 1 and L 1 being bonded to form an allyl moiety of a linear or cyclic alkyl allowing a nickel-allyl type 7 bond.
    [0004]
    4. Complex according to one of claims 1 to 3 wherein the Rlsoit Ria and R113 groups being identical or different, bonded or not with each other, and R'1 groups, R'la, R'lb and Filc being identical or different, whether or not linked together, are independently selected from alkyl groups having 1 to 15 carbon atoms, aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
    [0005]
    5. Complex according to claim 4 wherein the groups R1, Ria and R113 being identical or different, bonded or not with each other, and R'1 groups, R'la, R'lb and Filc being the same or different, bound or not, are independently selected from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl, adamantyl, substituted or unsubstituted, containing or not heteroelements; phenyl, o-tolyl, m-tolyl, ptolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4- methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or no, containing heteroelements or not.
    [0006]
    6. Complex according to one of claims 1 to 5 wherein the R2 groups and the R'2 groups, identical or different, are independently selected from alkyl groups comprising 1 to 15 carbon atoms, the aromatic groups comprising 5 to 20 carbon atoms; substituted or unsubstituted, containing heteroelements or not.
    [0007]
    7. Complex according to claim 6 wherein the R2 groups and the R'2 groups, identical or different, are independently selected from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl groups. tert-butyl, pentyl, cyclohexyl, adamantyl, substituted or unsubstituted, containing heteroelements or not; the phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl and 2-isopropoxyphenyl groups, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-bis (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or unsubstituted, containing heteroelements or not.
    [0008]
    8. Process for preparing a complex according to one of claims 1 to 7 comprising contacting at least one ligand comprising said ligand fragment consisting of P, N, S and O atoms, with at least one oxidation state nickel precursor (0), a precursor of the Xl group, a precursor of the group Let optionally a precursor of the Lewis base group L2.
    [0009]
    9. The method of claim 8 wherein the nickel precursor is selected from nickel (0) bis (cycloocta-1,5-diene), nickel (0) bis (cycloocta-1,3-diene), nickel (0) bis (cyclooctatetraene), nickel (0) bis (cycloocta-1,3,7-triene), bis (otolylphosphito) nickel (O) (ethylene), nickel (0) tetrakis (triphenylphosphite), nickel (0) tetrakis (triphenylphosphine), and nickel (0) bis (ethylene), alone or in admixture.
    [0010]
    10. Process for the preparation of a complex according to one of claims 1 to 7 comprising contacting at least one ligand comprising said ligand fragment consisting of P, N, S and O atoms, with at least one oxidation state nickel precursor (+11), in the presence of a precursor of the X1 group, a precursor of the L1 group, a reducing agent and optionally a precursor of the Lewis base group L2.
    [0011]
    11. The process as claimed in claim 10, in which the nickel precursor is chosen from nickel chloride (11), nickel (II) chloride (dimethoxyethane), nickel bromide (11) and nickel (II) bromide. (dimethoxyethane), nickel fluoride (11), nickel iodide (11), nickel sulphate (11), nickel carbonate (11), nickel dimethylglyoxime (11), nickel hydroxide (11), nickel hydroxyacetate (11), nickel oxalate (11), nickel carboxylates (11) such as, for example, 2-ethylhexanoate, nickel phenates (11), nickel (11), nickel trifluoroacetate (11), nickel triflate (11), nickel acetylacetonate (11), nickel hexafluoroacetylacetonate (11), allyl nickel chloride (11), deallyl nickel bromide (11), dimer of methallyl nickel chloride (11), allyl nickel hexafluorophosphate (11), methallyl nickel hexafluorophosphate (11), nickel biscyclopentadienyl (11), nickel bisallyl (11) and bismethallyl nickel (11); in their hydrated form or not, taken alone or in mixture.
    [0012]
    12. Use of a complex according to one of claims 1 to 7 or prepared according to one of claims 8 to 11 as a catalyst.
    [0013]
    13. A process for oligomerizing an olefin feedstock comprising bringing said feedstock into contact with a complex according to one of claims 1 to 7 or prepared according to one of claims 8 to 11, in the presence or absence of of solvent.
    [0014]
    The process according to claim 13 wherein the complex is used in admixture with a compound selected from the group consisting of tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbylaluminum compounds, aluminoxanes, organoboron compounds. , organic compounds capable of giving or capturing a proton, taken alone or as a mixture.
    [0015]
    15. The process of claim 13 or 14 wherein the feedstock comprises olefins having a carbon number of from 2 to 10.
    [0016]
    16. The method according to one of claims 13 to 15 wherein the reaction is an oligomerization reaction of ethylene.
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    2021-01-15| ST| Notification of lapse|Effective date: 20201214 |
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    申请号 | 申请日 | 专利标题
    FR1453817A|FR3020286B1|2014-04-28|2014-04-28|NOVEL NICKEL COMPLEXES AND THEIR USE IN A PROCESS OF OLEFIN PROCESSING|FR1453817A| FR3020286B1|2014-04-28|2014-04-28|NOVEL NICKEL COMPLEXES AND THEIR USE IN A PROCESS OF OLEFIN PROCESSING|
    EP15305336.8A| EP2939743A1|2014-04-28|2015-03-04|Novel nickel-based complexes and use thereof in a method for transforming olefins|
    CA2889386A| CA2889386A1|2014-04-28|2015-04-23|New nickel-based complexes and their use in an olefin transformation process|
    US14/694,216| US9308528B2|2014-04-28|2015-04-23|Nickel-based complexes and their use in a process for the transformation of olefins|
    JP2015090221A| JP6496602B2|2014-04-28|2015-04-27|New nickel-based complexes and use of harmful complexes in olefin conversion processes|
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